Process of chlorination



F. SPARRE AND W. E. MASLAND.

V PROCESS OF CHLORINATION.

APPLICATION FILED OCT. 31. I912. RENEWED MAR-111917.

1,379,367, P tented May 24,1921.

3 SHEETS-SHEET 1.

J TOR WITNESSES :HAA Neg/EN 2.1M m {M X. W Pwmm ATTORNEYS F. SPARRE AND W. E. MASLAND.

PROCESS OF CHLORINATION.

APPLICATION FILED 0m. 31. I912. RENEWED MAR. I, I9I7.

1,379,367. Patented May 24, 1921.

3 SHEETSSHEET 2.

}. WW1 as M will imam E. SPARRE AND w. E. MASLAND.

PROCESS OF CHLORINATION.

APPLICATION FILED 061131, I912. RENEWED MAR-1,1917.

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FIN SPARRE AND WALTER E. MASLANP, OF WILMINGTON, DELAWARE, AS SIGNORS 'IO E. I. DU PONT DE NEMOURS & COMPANY, OF WILMINGTON, DELAWARE, A COR- PORATION OF DELAWARE.

rnocnss or CHLORINATION.

Specification of Letters Patent.

Patented Ma '24, 1921.

I Application filed October 31, 1912, Serial No. 728,887. Renewed March 1, 1917. Serial No. 151,845.

To all whom it may concern:

Be it known that We, FIN SPARRE and WALTER E. MASLAND, of Wilmington, in the county of Newcastle and in the State of Delaware, have invented a certain new and useful Improvement in Processes of Chlorination, and do hereby declare thatthe'following is a full, clear, and exact description thereof. I

Our invention relates particularly to a .process of chlorination or halogenation of saturated hydrocarbons, that is to say, producing a chlorin or halogen derivatives by treatment with chlorin or halogen respectively, although it is applicable also to the chlorination of many other compounds.

The object of our invention is to provide a process of the kind above referred to, in which the process of chlorination may be carried out continuously and with a great de ree of rapidity, but with safety.

itherto, the process of chlorination has been ordinarily carried out by passing chlorin into a receptacle artly filled with the hydrocarbons, and su jecting the same to the action of chlorin carriers such as iodin, or to light, or both, in such a way that free spaces have been present over the body of liquid, thereby allowing the accumulation of gases over the surface of the liquid, or the reaction has been even conducted between the gases themselves. It has been found that when carried out in this manner the process frequently resulted in an explosion, owing to the fact that the reaction is effected at times very rapidly, and when a reaction takes ,place rapidly between two ,gaseous constituents, it is likely to result in an explosion.

Our invention comprises a process which will give better yields, a better control'of operations, and avoid the possibility of such explosions. In accomplishing ,th1s result, we cause the chlorin to be absorbed in the hydrocarbons in a dark chamber. 'Inasmuch as the reaction between the chlorin and the saturated hydrocarbon takes place only in the presence of li ht, it will be seen that the absorptionis e ected under conditions which will avoid any reaction between the chlorin and the hydrocarbon. Under these circumstances, there cannot be any cause for an explosion during the absorption ofthe ch10rin,as the explosions which have hitherli uid. So long as the reaction is effected- .within the body of the liquid, the danger of an explosion is eliminated, as the reaction could not, by any possibility, take lace so vlolently Or with local heating to t e ignition point within the body of the liquid as to result in an explosion. The reaction within the chamber referred to is earned out with a great degree of rapidity as we use, in connection therewith, sunlight or a source of blue light which has been,

found to be the most active in' efi'ecting the chlorination.

Furthermore, the reaction is. r .carried out without the necessity of any additional re-agents and without the presence of any chlorin carriers such, for example, as 1od1n or sulfur. In fact, wehave discovered that chlorln carriers are d1sadvan-.

tageous in effecting thereaction, owing to the possible danger in their action anddifficulty in controlllng the process. The process is, furthermore, carried out in such amanner that there are no mechanical losses, the hydrochloric acid produced in the reaction being recovered and any chlorin and hydrocarbon vapors that escape during the reaction being returned and utilized. The process is, furthermore, carried out man apparatus in which it can be readily regulated and with a minimum amount of labor. In carrying out the process, it' is merely necessary to control the amount of light ad mitted to the reaction chamber'an'd to contral the amount of chlorin admitted into the absorption chamber. These two manipula-' tions can be readily taken care of by one attendant. In order to carry out the process, we have provlded an apparatus which effects all of the results above referred to, and which has many new features which make it advantageous and valuable in the process of hlorination.

.While we may make use of many different kinds of apparatus for carrying out the process, for the purposes of illustration and p i as a preferred embodiment of theapparatus which may be used, we have shown only ne form of said apparatus in the accompan'ylng drawings, in whichhas Figure lie .1- side elevation of a portion of an apparatus used for carrying out the process;

Fig. 1 is a similar view of the remainder of said apparatus; v

Fig. 2 Is an end elevation of the apparatus shown in Figs. 1 and 1;

Fig. 3 is an end elevation of the entlre plant containing1 said apparatus, showing the arts somew at diagrammatlcally; and,

Fig. 4 is a plan view of a portion of the same. a

- In the drawings we have shown an opaque tower 1 having any suitable interior construction to effect the absorption of a gas in a liquid. This absorption tower has an inlet 2 at its top for liquid hydrocarbon, said inlet being connected to a discharge plpe 3 leading from a stoneware plunger pump 4 which withdraws the liquid from a tank 5 by means of a pipe 6. The tank 5 is charged with liquid through a lead funnel 7 connected to a stoneware stop-cock 8 supported in the outer end of an inlet pipe 9 leading lIlltO said tank. The stoneware pump 4 is operated in any suitable manner to'force a continuous current of the liquid into the top of the absorption to wer 1. Near the bottom of the tower there is provided an inlet pipe 10 for chlorin gas, leading from a series of chlorin bottles, 11, containing liquid chlorin. Stop-cocks 12 are provided on the tops of these bottles to permit the flow of chlorin gas to be readily regulated. The hydrocarbon liquid having absorbed the chlorin' gas, it is conducted out of the tower 1 at its base by means of aglasstube 13 leading into a stoneware pipe 14. The pipe 14 conducts the liquid to a manifold 15, to which are at-- fold 23, a similar set of glass tubes 24, and a;

manifold 25. 'As the liquid passes through the glass tubes 16, 20 and 24, the chlorin gas becomes combined with the hydrocarbons, giving off hydrochloric acid, and the process is so regulated that the yellow color of the chlorin gas will have disappeared when the liquid has passed out of the lowermost set of glass tubes 24. From the manifold 25, the liquid is conveyed by a pipe 26 to the tank 5, which may have a glass cover, if desired to increase the action of the light, and which is provided with a draw-ofl' cook 27 to draw the liquid off when the reaction is complete, that is to say, when the hydrocarbons have been sufficiently chlorinated. The apparatus is usually operated in such a manner, however, as to circulate the li uid through the absorption tower and the g ass tubes referred to until the required degree of chlorination has been efl'ected. Any gas which accumulates in the tank 5, which is principally hydrochloric acid gas, is conducted away by means of a pipe 28. This pipe 28 has connected to it a series of branch pipes 29, one of which communicates with each of the manifolds 15, 21 and 23 in order to convey away from said manifolds any gases which have accumulated during the reaction. The gases which have been thus obtained from the tank 5 and the manifolds 15, 21 and 23 are then conveyed through the pipe 30, to which is connected a pipe 30*, having a plurality of branches 30", one of which leads to each of the manifolds 17, 19 and 25. The gases which have thus been collected in the tank 5 and the various manifolds, are conveyed by means of the 30 to a glass condenser 31 having provlsion for'a water jacket 32 supplied with a cur rent of cold water by inlet and outlet pipes pipe gas is conveyed upwardly through said tower and is subjected therein to a current of water which is conveyed downwardly through the same from an inlet pipe 37 having a funnel 38 to receive a stream of water from a water supply pipe 39. This pipe 37 also has a water jacket 40 to condense as much as possible of the condensible vapors which fail to be absorbed in the tower 36. The vapors which are not absorbed in this manner are conducted from the pipe 37 in the reverse direction into a vapor collector 41 having a water jacket 42 provided with a water inlet pipe 43 and an outlet pipe 44 for the Waste water. The outlet pipe 44 from the water jacket 42 is connected to an inlet pipe 45 leading to the waiter acket 40 upon the pipe 37, and from the water jacket 40 a water discharge pipe 46 leads to the sewer. The vapor collector 41 is provided with a body of oil to absorb any of the hydrocarbon vapors which fail to be condensed in the other portions of the apparatus. At its end, the vapor collector 41 has a T-joint .47 from the top of which a vent pipe 48 valve 50 toermi-t the contents of the va collector to e drawn off at any time w on desired.

The water which flows downwardl through the tower 36 and which is to absorb the h drochloric acid gas and any chlorin gas t erein so as to thereby increase the concentration of the hydrocarbon vapors and condense the same under the cooling action of the water is conducted out of the said tower'together with the condensed hydrocarbons by means of a pipe 51, and through a spray nozzle 52 into the tank 5. TheJiquid containing hydrochloric acid gas and chlorin gas is thus brought into intimate contact with the ,body of chlorinated hydrocarbons within the tank 5, and thereby any chlorin present in the water is'abstracted by, and becomes absorbed in the hydrocarbons.

Any chlorin gas which fails to be absorbed by the hydrocarbons in the absorp-v tion tower 1 is conducted from the top thereof by means of a pipe 53 which is inclined upwardly from the top of the absorption tower to a pipe 54 which conveys the gas through a glass lantern 55, a pipe 56 and a pipe 57 to the tank 5, where the chlorin is, at least in part, absorbed by the hydrocarbons in said tank. The upwardly directed pipe 53 is provided with a water jacket 58 to condense any hydrocarbon vapors which. may have escaped from the top of the absorption tower. This water jacket 58 has a water inlet pipe 59, a vent 60, leading to the open air, and a water overflow pipe 61 leading downwardly therefrom to the sewer.

In orderto maintain the tank 5 as cool as possible, there is a water spraying pipe 62 located at each side thereof for spraying water on the sides of the tank. This water spraying pipe is supplied with a stream of water by means of a pipe 63 having a handoperated valve 64. The water thus sprayed upon the sides of the tank is collected in a trough 65 surrounding the bottom of the same, from which an overflow pipe 66 leads to the sewer.

The tank 5thus acts as an accumulator of all the liquid products of the apparatus, the hydrocarbons and the chlorinated hydrocarbons collecting in the top of the tank,

and the hydrochloric acid and water-collecting in the bottom thereof. The hydrochloric acid is conveyed from the bottom of said tank by an overflow tube 67 leading to a pipe 68, the top of which is open to the atmosphere and the bottom of which leads, by means of a ipe 69, to a stoneware reservoir 70 for receiving hydrochloric acid. The bottom of the reservoir 70 has a draw-off cock 71 and said reservoir is also supplied with an overflow pipe 72 leading upwardly from its bottom and discharging into a pipe 73, leading to the sewer.

The various water inlet pipes are provided with a supply of water from a common water inlet pipe 74 having a branch 75 leading to the pipe 59, a branch 76 leading to the pipe 63, a branch 77 leading to the pipe 33, a pipe 78 leadin to the pipe 43, and a pipe 79 leading to t e pipe 39. Over the glass tubes 16, 20 and 24, we have located a series of -mercury vapor lights 80 which are adapted to throw a blue light upon said tubes. The'mercury lights, 80 are supported in such a manner that the may be readily moved away when it is esired to have sunlight thrown upon the tubes. The entire apparatus is inclosed in a build ing 81 having lass panes 82 at the top and sides thereof adjacent to the portion of the apparatus including the glass tubes referred to. In order to control the amount of light coming through the glass panes, we provide a curtain 83 beneath the panes in the roof, and a curtain ,84 over the panes in the wall of the building. By a manipulation of the curtains 83 and 84 and the lights 80, theproper degree of light may be thrown upon the tubes in which the reaction is to The operation of the process may be sum: marized as follows:

When a quantity of hydrocarbons has been placed in the tank 5, the pump 4 is started and a constantstream of the hydrocarbons is caused to pass downwardly through the absorption tower l. The speed of this current may be. regulated by the speed of operation of the pump 4. The current of chlorin is then admitted from the chlorin bottles 11 by properly manipulating the hand-valves thereon until a proper amount of chlorin is admitted to the absorption tower, the proper amount of chlorin being determined by the complete disappearanceof the yellow color from the h drocarbons as the same leave the last series of glass tubes 24. Inasmuch as the absorptionof the chlorin is caused to take place in the hydrocarbons in a dark chamber, that is to say the tower 1, the absorption is effected before the reaction of chlorination begins. There is, consequently, no danger of an explosion 116 during the absorption. This is very important, inasmuch as an explosion in the presence of vapors would be very destructive. It is for this reason that the applicant has devised a process and apparatus of 120 such a character that the reaction will not take place in a chamber where there is free space for the collection of gases or vapors. The absorption having been elfe cted, the hydrocarbons containing the absorbed chlorin pass downwardly through the glass tubes where the light, which may be either daychlorinated hydrocarbons are then discharged into the tank 5. Any hydrochloric acid as which escapes from the liquid during the reaction and after the liquid. has been conducted into the tank 5, is-conveyed by means of the pipe 30 through the condenser vfor the purpose of returning the vaporized hydrocarbons, and then into an absorption tower provided with. a percolatin stream of water to absorb the hydroch oric acid gas and to condense a further quantity of the hydrocarbons. The water containing the absorbed hydrochloric acid as is then conducted to the tank 5 where it is sprayedthrough the body of hydrocarbons for the purpose of causing the hydrocarbons to take up from the same any absorbed chlorin as and also to remove the hydrochloric ac1d still remaining in solutlon in the hydrocarbons and chlorhydrocarbons in the tank 5. It will be understood that the water containing hydrochloric acid may also contain chlorin or from the various manifolds of the lass tubes in which the reaction is effected. ome of the chlorin thus conducted into the absorption tower 36 may also have emanated from the top of the absorption tower 1 from which the unabsorbed chlorin gas is led by means of a series of pipes into the top of the 1 tank 5. The liquid which is thus conveyed from thebottom of the tower 36 into the tank 5 may also contain any liquids condensed beyond the tower 36 in the condenser 40. Any gases which are not condensed in the condenser are led into the vapor collector where the uncondensedlhydrocarbon vapors are absorbed in a body of kerosene or similar hydrocarbons which maybe drawn ofi from time to time by the pipe 49. Any remaining gases or vapors are vented to the outer air by means of the ventA8. From the tank 5 the accumulated water containing hydrochloric acid is conveyed continuously to the storage receptacle from which it flows out continuousl from the bottom through the pipe 72. ny hydrocarbons or chlorhydrocarbons carried ofit' accidentally into the receptacle 70 will remain in the upper part of the same and may be drawn off as desired through the cook 71. The

height of the liquid in the tank 5 may be i treatment continues, some of the higher subg asowing to the'escape thereof from the tan 5 stitution products are formed in addition. If it is desirable to obtain onl monoand dichlor substitution products, t e a paratus is operated until about one-half o the hydrocarbons have been chlorinated. The

2. The process which comprises absorbing chlorin in-a body of liquid in the absence of light, and then chlorinating the liquid in such a manner as to avoid the maintenance of a body. of gas over the same.

3. The process whi 11 comprises chlorinating a body of hydrocarbon liquid in such a manner as to avoid the maintenance of a body of gas over the same.

4. The process which comprises absorbing chlorin in a body of hydrocarbon liquid in the absence of light, and then chlorinating the hydrocarbon liquid in such a manner as to avoid the maintenance of a body of gas over the same. t

5. The process which comprises chlorinating a body of liquid in such a manner as to avoid the maintenance of a body of gas over the same in the presence of light.

6. The process which comprises absorbing chlorin in a body of liquid in the absence of light, and then chlorinating the liquid in such a manner as to avoid the maintenance of a body of gas over the same in the pres ence of light.

7. The process which comprises chlorinating a body of hydrocarbon liquid in such a manner as to avoid the maintenance of a body of gas over the same in the presence of light. 1 8. The process which comprises absorbing chlorin in a body of hydrocarbon liquid in the absence of light, and then chlorinating the hydrocarbon liquid in such a manner as to avoid the maintenanceof a bod of gas over the same in the presence of lig t.

9. The process which comprises chlorinating a body of liquid in such a manner, as to avoid the maintenance of a body of gas over the same in the presence of a blue light.

10. The process which comprises chlorinating a body of hydrocarbon liquid in such a manner as to avoid the maintenance of a body of gas over the same in the presence of a blue light.

11. The process which comrises chlorinnating a body of liquid in sue a manner as to avoid the'maintenance of a body of gas over the same in the absence of chlorin carriers.

I in water, and mixing the water with the chlorinated hydrocarbon.

14. The rocess which comprises chlorinating a hydrocarbon liquid thereby causing the escape of a gas, absorbing escaping gas in Water, and mixing the water with the chlorinated hydrocarbon, while keeping the latter cool.

15. The process which comprises absorbing chlorin in a hydrocarbon, chlorinating the hydrocarbon liquid thereby causing the escape of chlorin, bringing unabsorbed chlorin gas into contact with water to absorb it, and mixing the water with the chlorinated hydrocarbon.

16. The process which comprises absorbing chlorin in a hydrocarbon, chlorinating the hydrocarbon liquid, thereby causing the escape of chlorin, bringing unabsorbed chlorin gas into contact with water to absorb it, and mixing the water with the chlorinated hydrocarbon while keeping the latter cool.

17. The process which comprises absorb-- ing chlorin in a hydrocarbon, chlorinating the hydrocarbon liquid thereby causlng the escape of chlorin gas and hydrochloric acid the escape of a gas, absorbing escaping gas in water, mixing the water with the chlorlnated hydrocarbon, and preventing the escape of the unabsorbed gas.

20. The process which comprises chlorinating a hydrocarbon liquid thereby causing the escape of a gas, absorbing escaping gas in water, mixing the water with the chlorinated hydrocarbon, while keeping the latter cool, and preventing the escape of the unabsorbed as.

21.- he process which comprises chlorinating a hydrocarbon liquid thereby causing the escape of a gas, absorbing escaping gas in water, condensing and preventing the escape of hydrocarbon vapors, and mixing the Water with the chlorinated hydrocarbon.

22. The process which comprises chlorinating a hydrocarbonliquid, thereby causing the escape of a gas, absorbing escaping gas in water and condensing and preventing the escape of hydrocarbon vapors, and mlxing the water with the chlorinated hydrocarbon, while keeping the latter cool.

23. The process which comprises absorbing chlorin in a hydrocarbon, chlorinating the hydrocarbon liquid, bringing unabsorbed chlorin gas into contact with water to absorb it, and therebycondensing and preventing the escape of hydrocarbon vapors, and mixing the water with the chlorin- V ated hydrocarbon.

24. The process which comprises absorbing chlorin in a hydrocarbon, chlorinating the hydrocarbon liquid, bringing unabsorbed chlorin gas into contact with water to absorb it, and thereby condensing and preventing the escape of hydrocarbon vapors, and mixing the water with the chlorinate ll hydrocarbon while keeping the latter coo 25. The process .which comprises chlorinating a hydrocarbon liquid, thereby causing the escape of a gas, absorbing escaping gas in water, and thereby condensing and preventing the escape of hydrocarbon vapors, mixing the water with the chlorinated hydrocarbon, and recovering by subsequent condensation unabsorbed and uncondensed the escape of a gas, absorbing escaping gas in water, and thereby condensing and preventing the escape of hydrocarbon vapors, mixing-the water with the chlorinated hydrocarbon, while keeping the latter cool, and recovering by subsequent condensation unabsorbed and uncondensed gas.

27 The process which comprises chlorinating a body of liquid in such a manner as to avoid the maintenance of a body of gas over the same in the presence of light containin blue rays.

' 28. he process which comprises chlorinating a body of hydrocarbon liquid in such a 26. The process which comprises chlorin-' ating a hydrocarbon liquid, thereby causing manner as to avoid the maintenance of abody of gas over the same in the presence of light containing blue rays.

29. The process which comprises halogenating a body of hydrocarbon liquid in such a manner as to avoid the maintenance of a body of gas over the same.

30. The process which comprises absorbing a halogen in a 'bodyof hydrocarbon liquid 1n the absence of light and then halogenating the liquid in such a manner as to avoid the maintenance of a body of'gas over the same.

31. The'process which comprises halogen- 33. The process which comprises -absorbing a halogen in'a liquid hydrocarbon under such conditions as to avoid a reaction between the halogen and hydrocarbon, and conducting the liquid mixture into a reaction chamber having conditions established therein such as to bring about a reaction within the liquid between the hydrocarbon and the halogen.

34. The process which comprises absorbing a halogen in a liquid hydrocarbon in the absence of light to avoid a reaction between the halogen and hydrocarbon and conducting the liquid mixture into a position to be reacted upon by light under conditions to bring about a reaction within the liquid between the hydrocarbon and the halogen.

35. The process which comprises bringing together in a mixing chamber a halogen and aliquid hydrocarbon so as to mix the same under conditions such as to avoid reaction,

and then transferring the mixed substances to a reaction chamber having conditions es tablished therein such as to bring about a reaction, then returning the product to the mixing chamber, adding more of the halogen and again transferring the mixture to the reaction chamber.

36. The process which comprisesbringing together in an opaque mixin chamber a halogen and a liquid hydrocar on so as to mix the same under conditions such as to avoid reaction, and then' transferring the mixed substances to a transparent reaction chamber having conditions established therein such as to bring about a reaction, then returning the product to the mixing chamber, I

adding more of the halogen and again transferring the mixture to the reaction chamber.

37 The process of. chlorinating hydrocarbons which comprises absorbing a halogen in a liquid comprising a hydrocarbon under such conditions as to substantially avoid a reaction between the halogen and the hydrocarbon, separating the resulting liquid from unabsorbed halogen, and then causing the hydrocarbon to react with the halogen carried thereby. v

' 38. Th process of chlorinating hydrocarbons, which comprises saturating with chlorin a liquid comprising a hydrocarbon under such conditions as to. substantially avoid a reaction between the chlorin and the hydrocarbon, separating the saturated liquid from unabsorbed chlorin, and then causing the hydrocarbon to react with the chlorin carried thereby.

In testimony that we claim the foregoing we have hereunto set our hands.

FIN SPARRE.

WALTER E. MASLAND. I

Witnesses: J DONALD R. MORTON,

CHAS. E. WEBB, Jr. 

